Chapter 2 .

Cast Irons

Introduction
This chapter is an expansion of the material in Chapter 9 secrion G (pp. 305-315) of the textbook. There is some overlap here with that material. but most of this chapter contains new material and refers to the text where appropriate. CAST mONS

From a commercial point of view the most important cast alloys are cast irons. From a scientific point of view the nature of the solidification of cast irons is extremely interesting and not completely understood. Cast irons are essentially ternary alloys of FeC-Si of near eutectic composition. To understand the role of silicon in cast irons it is useful to fITStexamine the binary Fe-C phase diagram shown in Fig. 9.64, p. 306 of the text, Notice that liquid eutectic iron (4.3%C) may solidify as either austenite + graphite or as austenite + carbide. The carbide (called cementite. Fe3C) fonns at I 148C. which is 6C below the temperature of formation of the graphite. This temperature difference will be termed, aT o-c. as indicated on Fig. 9.64. When the eutectic forms with graphite we have a gray iron and when it forms with Fe3C we have a white iron. These names evolved because of the appearance of the fracture surface of the two irons. The graphite microstructure of the gray irons produces a fracture surface which has a gray shading compared to a quite white appearance observed for the fracture surfaces of white cast iron. The gray appearance of a grey iron results because the fracture occurs through graphite flakes so that the exposed fracture surface is over 90% pure graphite. In white iron the fracture surface is predominately Fe3C which is quite white in appearance. The graphite is the thermodynamically stable phase whereas the Fe3C is actually a metastable phase since it forms at a lower temperature. For kinetic reasons it is more difficult for the graphite to form than the Fe3C. Consequently when one solidifies a pure binary iron-carbon eutectic alloy in a normal manner the eutectic solid contains Fe3C. The Fe3C eutectic is often tenned ledeburite. The major effect of silicon is to increase the value of aTO-c above 6C as is shown in Fig. 9.65. As aTO_C increases the thermodynamic driving force (aG. aSoaTo_cl for forming graphite prior to forming Fe3C is increased and. hence. the probability of forming a graphite eutectic rather than a carbide eutectic is increased. Hence. Si promotes the formation of graphite. This important effect is discussed below with the aid of ternary diagrams. A few other elements such as Ni also produce the same type of effect, There are four main types of cast irons each of which is characterized by a distinctive microstructure as listed in Table 9.9. Table 9.9 The four cast irons and their microstructures. Type Morphology of carbon rich phase Gray Flake graphite Ductile Nodular (spherical-like) graphite White FeC as both plate dendrites and within a rod entectic Malleable Nodular (sherical-like) graphite

The microstructure of cast irons consists of a carbon-rich phase in an iron-rich phase. The iron-rich phase often consists of ferrite or pearlite. As shown in Table 9.9 the carbon-rich phase is graphite in all of the cast irons except white iron, where it is Fe3C. Examples of typical gray and nodular cast iron microstructures are shown in the text as Fig. 9.71. In
both of these irons the graphite forms by precipitation directly from the liquid iron during

the solidification process. Of the four irons, malleable iron is unique in that the graphite is
fotmed by heat treatment. Malleable iron is produced in a two step process where one first

produces a casting of white iron and then heatrreats the iron at suitable temperatures and
times to cause the metastable Fe3C to decompose, thereby producing nodules of graphite. The surfaces of the nodules of graphite in malleable cast iron are generally less smooth than

in ductile cast iron and one can usually distinguish between the two microstructures fairly
easily (see p. 88, 8th Edition Met. Hdbk, Vol. 8). 1 % C2 3 4 Fe '-~""~---'-~-'--~--'TT"" .. tectic Trough (%C+I/3%Si=l.3)

The approximate composition ranges of the four types of cast irons are given in
Table 9.10. Notice that the sulfur

\-\';~
\
-

compositions of nodular iron is significantly less than for the other irons. The Mn and P compositions do not differ
appreciably and the Si and C

\
White (Malleable)

Grey

- \- '---'rT---\
Hypoeut<=/=>Hypereuteetic

ranges may be compared nicely

by plotting them on the ternary

composition plane as shown in

Fig. 9.73.

FiglU'~9.71. A plot offlu. composition rang~for flu. 4 tyPU of ClJSl irO#l Ilp01IIM composition plJvM.

Table 9.10 Composition range of cast irons (wt.%) Name Grav NOdular White, Malleable %C 2.5-4.0 j-4 \.8-3.6 %Si 1-3 %Mn .4-1 %S .05-.25 .Ojmax .06-.2 %P .05-\.0

i.a-z
5-\.9

.z-.9
.2-.8

.Olmax
.06-.18

Ternary FewC_Sj Phase EQuilibria

There are two different ternary phase diagrams which are important to the study of cast irons, the stable system, Fe-graphite-Si, and the metastable system, Fe-Fe3C-Si. There is considerable experimental difficulty in determining both of these ternarydiagrams and consequently they are not well established. A reasonable estimate of the Fe-graphite-Si

ternary diagram is presented in Fig. 9.74, which is drawn with the composition axes
arranged similar to Figs. 25 and 32 of Chapter 9A. A Class II 4 phase equilibrium plane occurs at - I 165C and has the reaction L + a ... Y+ graphite. As Si is added the eutectic

trough rises slowly in temperature and also shifts to lower C concentrations.

temperature as Si is added.

This is

probably the most important feature of the diagram for the study of cast irons. In contrast

to this behavior it is known that the eutectic trough in the Fe-Fe3C-Si diagram drops in 'f, ',C-_.'
Before discussing the Fe3C system further it is helpful to redraw the Fe-graphite-Si system with the Si axis reversed so that it comes out of the page as is shown in Fig. 9.75. The Fe-graphite and Fe-silicon binary diagrams are shown with dashed lines. The eutectic

trough line extends downward in temperature from point L on the 4-phase plane to E on the

pure Fe-graphite binary. If this trough line is projected down onto the composition plane as shown, it is found to follow the equation (64),
% C+ 1/3 % Si=4.25 (9.63) Consider the alloy of composition Co. When it cools down it meets

the liquidus at point a and one sees

that the primary dendrite tips will

consist of"( phase (austenite) at

, ,
~ 11

, , , ,

~~_

composition b. It should be clear from the diagram that as long as the value of Co lies to the left of the line given by Eqn. (9.63) the

, , , , , , , , , , , , , , , , , , 9\2, \ , , , , , ,
,
s'

primary dendrites will be austenite. Mathematically this

requires % C + 1/3 % Si < 4.25 (9.64)

(Note: If % Si = 0 then % C < 4.25 where 4.25 is the % C in the

pure Fe-graphite eutectic). The

value on the left of Eqn. (9.64) is called the carbon equivalent, CE, CE=%C+I/3%Si (9.65)

A cast iron having CE < 4.25 is

Figure 9.74. The F~-graphiJe.Si ternary sptu:e dlQ.gram.

said to be hypoeutectic and one expects such irons to display primary austenite dendrites. If CE

> 4.25 the alloy is hypereutectic and will meet the liquidus surface to the right of the eutectic trough; hence, its primary
dendrites are expected to be graphite, if

no nucleation barrier exists for the formation of the graphite phase. Because graphite is about three times
lighter than iron the primary graphite dendrites may float to the surface (called "kish" graphite) and produce an

'
.Q

P
.,

I. \............ <s-;

,Iron-Graphite Binary

:1

,~ II

::1'

---

__ ... ...
...:>.__ .
_........

unwanted phase separation. Hence the CE of a cast iron is an important parameter for characterizing the iron.
Equation (9.65) is plotted on Fig. 9.73

''''t'' " -- .... ........., "," i'" ~!;~~ft -~:?':, ~

"II

__

Co

......
.........

Eutectic trough coming down from 4-phase plane

I

;.

,,"

1154"<:

E ~

t
"

I: I: I:

~l'~o-::;7-

Gr~~"':te .......

and illustrates that most cast irons are

hypoeutectic. Consider now how the alloy of

h' .$;"-'",
)T\' I I , I, \ " I ~. :,

.'

LU~Jtl16~~=~;-=-::='I\ Class [( 4- ase Plane

a+L--+1
Or

"

composition Co would be expected to

solidify based on the ideas presented in Chapter 9A. As the primary 1

" " " rl:

..c_

%C + 1/3 % Si = 4.25

dendrites fatten out the interdendritic

~:

Figure 9.75. Alternate view o/IM Fe-graphiJe-Si space diagram.

'Y + Or

Eutectic

...... ;;~~~:===:~
'Y 'Y

liquid would become enriched in C (as shown on Fig. 9.75 the % Si at points a and b is nearly the
interdendritic liquid composition would follow the

same, kSi - I, so that the % much). Si liquid interdendritic liquid doesn't changeSi in theThe liquidus surface from a to 1 where it encounters the eutectic trough. As shown on Fig. 9.76 if

Figwe 9.76. Possible solid-liquid inlerface morphology apectedfrom phase diagram of Fig. 9.75.

nucleation and coupled growth of the Gr + 't eutectic occurred easily, one would expect the eutectic solid to nucleate and grow as a shell around the dendrites with the eutectic liquid

following the trough line from L to E and the 1

component of the Gr + "1 eutectic following the line l' to E'. In this alloy system, however, the eutectic solid only forms as coupled growth of Or + "f in gray cast iron. In both ductile cast iron and white cast iron different growth modes occur, as discussed below. And. in gray cast irons the coupled eutectic growth does not occur as shells around the austenite dendrites as shown on Fig. 9.76. Instead, the Or + r eutectic fOnDS as

spherical balls (called cells or colonies) which nucleate in the interdendritic liquid and grow outward encasing the austenite dendrite arms within their spherical volume as they grow. See Fig. 9.68(b) and Fig. 9.69 on page 311 of the text and the discussion there. The spherical eutectic cells are an example of facetedlnonfaceted coupled eutectic growth. The graphite within the spherical cells has the shape of flakes and is interconnected in an irregular geometry throughout each cell, as illustrated in Fig. 9.69. The resulting iron is a gray cast iron and many of its physical properties are controlled by the shape and interconnectivity of the graphite. In particular, the shape of the graphite flakes leads to stress concentrations at their sharp edges and causes gray iron to be quite brittle. On the other hand the interconnectivity of the graphite gives rise to the excellent damping capacity of these irons and their superior thermal conductivity over steels. White Cast Iron In a white cast iron the L + S ~ yPeritectic carbon precipitates from the liquid Fe-Graphite Trough Line as Fe3C rather than graphite and Eutectic Trough white irons are quite hard but very brittle. The same cast iron may be L + Or surface --r made to solidify white or gray by , C,L+Fe3csurface control of the solidification _:o.~I , 1154"C A constant , I .... , / process. To understand why this temperature on the ,,-~.,-r_--- .> --'11470C .. is so it is helpful to consider the austenite liquidus combined ternary diagrams for Feswface Fe-F'JC graphite-Si and Fe-Fe3C-Si in the region of the eutectic troughs, Fig. Eutectic trough 9.77. The important point to see T = t147 - 13.3 Si here is that the eutectic trough on %C-+ the graphite system rises in t temperature as Si is added, %C + 3 %Si = 4.25 -+'.A" whereas in the Fe3C system it drops in temperature. This effect is FiglU'f!9.77. A combined terNJrY diagram showing tM eutectic tro"gm of both the Fe- graphite-Si and Fe jC -Si systons. illustrated further in Fig. 9.78 by displaying isopleths of the trough regions at % Si increasing from 0 to 3%. As the Si increases the temperature difference between graphite and Fe3C troughs, &TG-C, ncreases significantly, as shown. Note that i

--- -- ----

----

-_._---

---

both trough lines lie on the austenite liquidus surface with the FeC trough lying at lower

temperatures and higher C compositions.

L L

L+l

L+Gr .25...1154

L
+ &TO/C
1.5%Si

Or
38%C 1165
.......1107

&T~I;r- 4.3 - -1147

0%

----3:-97%(;-3%Si

Si

Figwt! 9.78. Three isopleths through the combiNd Fe-graphite-Si and Fe-Ft!JC-Si syslemsal % Si = 0,1.5 and 3% (64).

In general, it is difficult for the carbon rich phase (Fe3C or graphite) to nucleate from the liquid iron lying between the austenite dendrites of cast irons. This means that the liquid will need to supercool below the equilibrium transformation temperature by some amount. AT. in order to supply the free energy, AG =AS-.1.T. to cause the carbon rich phase to nucleate. This idea is illustrated in Fig. 9.79. When an alloy of composition Co

reaches the austenite liquidus at point 1 the austenite dendrites grow (usually after only a
small supercooling and recalescence) causing the interdendritic liquid to become enriched in C. As shown by the arrows the interdendritic liquid composition will run down the

austenite liquidus surface and because nucleation is difficult the liquid supercools below the
trough points of both the graphite at a and the Fe3C at b. For liquid at point 2 on Fig. 9.79

the free energy available to form the graphite eutectic is .1.Go'" .1.S.1.Toand to form the Fe3C eutectic it is, .1.Gw ....1.S.1.Tw. One would normally expect the gray eutectic to nucleate and grow in preference to the white eutectic because .1.Go>.1.Gw. However, it is sometimes more difficult for graphite to nucleate and start the graphite eutectic cells
growing than it is for the Fe3C to nucleate. Addition of Si increases the &Td&Tw ratio and

favors the graphite nucleation, and this is the primary reason for the Si addition in cast irons. The question of which form the C takes, graphite versus Fe3C, is a bit more complicated. It requires consideration of
both nucleation and growth phenomena.
Gray trough White trough

Before discussing this it is first useful to describe white cast iron structures. White cast iron structures consist of
plates of Fe3C surrounded by a rod eutectic

microstructure consisting of rods of austenite in an Fe3C matrix as shown at the lower

right of Fig. 9.84. In hypoeutectic irons a white cast iron solidifies from the liquid in Isopletli7--

essentially a three step process. First the Traces --:-. austenite dendrites nucleate and grow throughout the casting volume. The
interdendritic as illustrated liquid becomes enriched in C on Fig. 9.79 and eventually

Fe3C nucleates at compositions below the trough point, such as point 2. After

Figuu 9.79. Trough region of Fig. 9.77 showing soJidi[/.CaJion path of inJerdendTilic liquid.

nucleation dendrites of Fe3C shoot rapidly throughout the interdendritic liquid. These Fe3C dendrites have a plate morphology as shown schematically in Fig. 9.80. By a branching process the dendrites fan out from each

point of nucleation and grow around the austenite dendrites. Their rapid growth liberates
considerable latent heat and drives the interdendritic liquid temperature up. Their higher C

composition depletes the interdendritic liquid

of C and their near zero Si composition increases the interdendritic Si content. The net effect is to shift the interdendritic composition
and temperature back up to the Fe-Fe3C-Si Side View End View
ofFejC

eutectic trough point as shown by arrow 3 on

Fig. 9.79. The third step now occurs. The liquid trapped in between the Fe3C plate dendrites begins to solidify by coupled eutectic growth. As previously mentioned the ....Fe3C

eutectic is often called ledeburite. The eutectic

Ftgwe 9.80. Shape of the plaledendrites which form in white cast irons.

morphology is of the regular type and in these ternary alloys consists of rods of austenite in an FC3C matrix. As shown in Fig. 9.81 the appearance of the ledeburite part of white irons depends strongly on how the sample was

sectioned. The rods only show their characteristic cylindrical geometry on sections close to Because of sectioning problems the rod structure is often not real apparent, as in Fig. 9.84. Note that pictures of cast iron are made at room temperature where the austenite does not usually exist Hence the austenite of the primary dendrites, of the eutectic cells in gray iron and of the rods of ledeburite in white iron will have transformed into one of the following: ferrite plus FC3C. or ferrite plus graphite, or pearlite. or bainite. or martensite, depending on silicon content and on cooling rate after solidification.
A-A in Fig. 9.81.

Gray versus White Cast Irop It is often found that a given cast iron will
solidify gray at slow cooling rates and white at high Plate Dendrites A (End view)

cooling rates. It is also found in laboratory experiments that as the growth rate increases a transition in structureoccurs from gray to white iron. These results may be understood by consideration of
Fig. 9.70 in the text. On this diagram the temperature at the growth front is plotted for the two types of structures. The line labeled graphite gives

o
o o

the temperature at the liquid/eutectic cell interface.

The equation of this line would be given by an equation similar to Eqn. (9.46), which would apply to the coupled irregular eutectic growth of the cells.

00 000 0 0 0 0 0

The line labeled cementite gives the temperature at

the liquidlFe3C plate dendrite tips. The equation of

View of the rod eutectic

along section A-A

this line would be given by an equation similar to FiglUe9.81. ThutrllCtlUeoflltalpartofawhilecast Eqn. (12.10) derived in Chapter 12. The curves iTt'" which lies between the austenite dendrites. reflect the fact that as the growth rate increases the interface temperature must drop in order to provide more free energy to transform the liquid to solid at the increasing rate. The key idea is that the front of the structure which can grow at a higher temperature will lead the other structure and crowd it out. Suppose that both a eutectic cell front and an array of Fe3C
dendrites are growing next to each other in a pure Fe-C alloy (no silicon, solid lines on Fig. 9.70). At growth rates greater than 10-4 cm/s the growth front temperature of the Fe3C dendrite array is greater and hence the dendrite tips will grow ahead of the cell front into the liquid. This aliows the dendrites to branch across in front of the cell front and crowd out the cell growth. At rates below 10-4 the argument is reversed and the cell front crowds out the Fe3C dendrite array. The addition of Si increases the aTclG value as discussed above.

The ATc/G value appears on Fig. 9.70 at zero growth rate. Hence, as shown by the dashed curve addition of Si raises the cross over velocity so that one must grow much faster to favor white iron structures. Hence addition of Si promotes formation of gray iron by both a thermodynamic effect (increasing ATc/G) and a kinetic effect (shift of crossover to higher

velocities).
ironsreadpp.

For further discussion of this transition and for a discussion of nodular cast
311 to 315 of the text.

The flakes in gray iron are known to grow with their a axis parallel to the growth direction, whereas the graphite is growing parallel to the C axis in spherulite growth. The elements Mg and Ce are able to force this change in growth axis, but we do not understand how. Graphite grows with a faceted interface as shown in Fig. 9.IO(a), and it is apparent that if solute atoms tended to absorb preferentially at the ledges they could poison this type of growth. Research work using radioactive sulfur and scanning Auger analysis has

shown that the S in cast irons tends to absorb on the broad faces of the graphite flakes in gray iron but S is not observed on the surface of the nodules in nodular iron. As mentioned above the sulfur level must be kept low in ductile cast iron. In addition, recent experiments have shown that nodules will fonn in high purity Fe-C-Si alloys without
addition of Mg or Ce. Hence, a recent theory of the role of Mg is that it does 2 things: I. It acts as a scavenger, removing S and thereby promoting C-axis growth of the graphite because the S would no longer be able to absorb on broad faces of the flakes and prevent growth outward.

2.

It somehow provides nucleation sites for nodular formation, perhaps by forming a carbide which becomes less stable on cooling and decomposes to liberate nascent carbon which acts as the nucleant.
Practice55

Inoculant

In the production of both gray and ductile cast iron it is common practice to add an
inoculant to the transfer ladle or to the pouting stream into the casting. We will discuss the function of the inoculant for gray and ductile irons separately. Qray - In gray irons the addition of the inoculant increases the cell count and thereby increases the tensile strength of the iron. For example. increasing the cell (or colony) count from 1000 to 3000 per inch2 increases the tensile strength typically from 28 to 32 ksi (193 to 221 MPa). In addition, increasing the cell count will decrease the chilling

tendency of gray cast irons. As discussed above, white iron tends

to

form in preference to

gray iron at higher solidification rates. As the cast metal freezes inward from the mold wall

the solidification rate decreases. Hence, it often happens that metal near the wall will solidify as white iron and a transition will occur to gray iron away from the wall where the solidification rate has become lower. The casting then contains both gray and white iron and is termed "mottled". The white cast iron is very hard and brittle so that mottled irons
can present problems with low toughness as well as machining problems. The depth in the

mottled iron near the wall which is white iron is often referred to as the chill depth, and this
chill depth is influenced by the cell count. Table 9.11 presents some data on the influence of an inoculant addition upon chill depth. It is seen from the data of Table 9.11 that the

addition of the inoculant increases the cell count and significantly reduces the chilling
tendency. The inoculant accomplishes this effect by reducing the supercooling required to nucleate the gray structure. As may be appreciated from Fig. 9.79 if ATo for nucleation is kept small enough, the gray eutectic will form before the liquid composition reaches the

Table 9.11 Effect of inoculan: addition upon chilling tendency

Amount Inoculant Added Small Medium -Lame Ceu Count (No/m2) 300
Chill

Depth

1/4"
I Ib

500
4700

Fe-Fe3C-Si trough. Also, reducing the super-cooling will teduce the velocity of Fe3C dendrites if they do form, thereby causing the transition to gray iron closet to the mold wall.

The inoculant is an alloy of iron-silicon called ferrosilicon to which a controlled amount of minor elements have been added. Table 9.12 presents some typical compositions. The mechanism by which the inoculant increases the nucleation rate of the graphite colonies is not certain. Much research has been done on this problem and the best current theories58 are that the active nuclei are CaS and the role of AI is uncertain. Table 9.12 Composition of some cast iron inoculantst?
Name InocuI. Si

r.a
.4

IAI

1St

Grade 75 Ferrosilicon Strontium 77 Ferrosilicon Calcium Silicon 160

1.8 .3 1.7

Fe Bal

.2
130

.7
0

" "

Ductile - The commercial production of ductile cast iron employs two additions to the melt, first the nodularizing addition. and then the inoculating addition. The nodularizing addition generally adds Mg as a ferrosilicon alloy and its function is to cause the graphite to form nodules rather than flakes, as discussed above. This addition is made to the furnace melt or the transfer ladle. The inoculating addition in ductile iron is quite
similat to that in gray iron. The inoculating alloys are essentially the same as for gray irons (with some exceptions, e.g., calcium-silicon is not effective) and they serve to both increase the nodular count and improve the spherical quality of the nodules. This addition

is made either to the transfer ladle, or the stream going into the pouring cup or sometimes
placed in the gating system which connects the pouting cup to the mold. The effectiveness
1noculated after holding

of both

Inoculated immediatel after nodularizing addition

the nodularizing and the inoculating additions tends to deteriorate with time, an effect often referred to as "fade". The fading tendency of an inoculant is
shown in Fig. 9.82. In these

experiments

the inoculant

was

oL_-=::::;====...----.:::::::: .... _
o
nodulQl'

added either immediately after the

5 Figwe 9.82. Fffe-Cltftime

15

nodularizing addition, or after a

holding time. It is seen that the

Holding Time (minutes)

of inocKlation on

fading tendency

is less if the

count/ode

59.

inoculant is added aftet holding.

This fading tendency is an important problem in cast iron foundry practice as fading times of 10 to 15 minutes are not unusual and one must therefore insure prompt pouring of metal after inoculation. The cause of this fading is not well understood, but is generally thought to be due simply to oxidation of the active ingredients, Mg in the nodulizer and Ca in the inoculant. Figures 9.83 through 9.85 illustrate some of the above ideas. Figure 9.83 is a photomicrograph at 47x showing the cross section of a gear tooth in a gear cast from gray iron. It is seen that in the upper right of the section a region of white iron has formed. This white iron is at the comer of the tooth. the point where the cast metal solidified most
Grey

I Lacy Spherical Graphite Fe3C Plate Dendrite Ledeburite

Pearlite Eutectic

.-I

Figure 9.83. Cast iron geM tooth showing white iron at corner of tooth: (47x)

Figure 9.84. Transition. zone at gray/white inJeiface.

rapidly. and most likely is the result of the chilling effect mentioned above. The transition zone between the white and gray iron is shown in Fig. 9.84. An unusual form of lacy spherical graphite has formed at this zone. The typical gray structure of graphite flakes in a pearlite matrix is present at the upper left. The white structure at the lower right consists of large plates of carbide which form as plate-like dendrites surrounded by the Fe-Fe3C eutectic. The Fe in this eutectic forms originally as austenite and in some regions it transforms to pearlite on cooling while in other regions it becomes thickened carbide, Fe3C. plus fenite. Figure 9.85 illustrates two further characteristics common in gray cast irons. Small gray colored regions of inclusions, mostly MnS, are shown at (4). The light region containing dots at (3) is a ternary phosphide eutectic called steadite that occurs in irons containing sufficient P. This phase has a low melting point and therefore solidifies at

f1.... -----------------------------------

the base of the dendrites and shows a characteristic concave-out curvature. Apparently, the

eutectic is a rod-type. A relatively recent development in cast irons is the use of a cast iron termed
"compact graphite iron". These irons60,61 have a graphite shape intermediate between normal flake graphite and the nodular (spherical) graphite of ductile iron. The graphite shape looks more like flake graphite than nodular graphite in the optical microscope, but it

is much fatter and shorter in length than typical flakes. (Note: it is sometimes called
vermicular or "worm-like" in the U.S. foundry literature.) These irons are attractive for

several reasons. They have considerably higher tensile strengths than gray irons, but slightly lower tensile strengths than ductile irons. They can be produced with lesser amounts of nodularizing additions, or by strong desulfurization plus rapid mold solidification. They are much less sensitive to fading than ductile irons and they are less sensitive to formation of shrinkage cavities than ductile iron.

Gray Region showing: (1) Graphite Flakes (2) Pearlite Matrix (3) Steadite _____ [Iron-Phosphide Eutectic]

(4) MnS Inclusions

Figure 9.85. lnli!rior region of geM. (405x)

CQolio& CurVes

Consider a hypoeutectic cast iron. A cooling curve is obtained by placing a thermocouple in the melt and recording the temperature as a function of time while the liquid solidifies around the thermocouple tip. A typical cooling curve is shown in Fig. 9.86. To understand what is occurring here consider the ternary space diagram of Fig.
9.87 where the alloy composition is located at Co. When the temperature of the liquid falls

to point a the liquidus surface is reached and austenite dendrites with a composition
corresponding to point b will begin to solidify. These growing austenite dendrites produce

a latent heat which results in the upper arrest temperature of the cooling curve. As explained previously the rip temperature of the dendrite is near to the liquidus temperature. The thermocouple effectively measures the temperature of the dendrite tips advancing toward it, because of the quite low gradient in the liquid. Hence, the observed arrest temperature is quite close to the liquidus temperature of the alloy.

10

As the dendrites grow the interdendritic liquid between them becomes entiched in both Si and C and this liquid follows a path along the liquidus surface such as a-I or a-2 until the eutectic trough is encountered. At this point e<i graphite will nucleate if appropriate nuclei are present and eutectic cells will begin to grow. ~ Generally some supercooling will be required

Austenite Dendrites

Fonn

~~~...J
Eutectic

Range ofEquil. Eutectic

Temps.

Nuclea the evolving latent heat raises the temperature of Tlme r-r-ethe liquid back up to the growth temperature of the advancing Pe-Gr growth fronts, thereby FiglU'e 9.86. Typical cooling CIITW! lOT a hypoeuuctic gray iron. producing the temperature rise shown on the cooling curve of Fig. 9.86. If the cooling rate is sufficiently fast the supercooling prior to formation of Or may be increased enough to nucleate Fe3C rather than graphite, in which case the Fe-Fe3C eutectic will form (white cast iron) and the arrest temperature for the eutectic will occur at lower temperatures on the cooling curve.
to

nucleate the graphite, and so, after nucleation

A considerable amount of research has been done on determination of the liquidus surface of cast iron alloys. This work has established that when the liquidus isotherms are
projected onto the composition plane they lie parallel to each other and follow the equation, CEL = % C + 1/4 % Si (9.66) where the % values are by weight, see Fig. 9.87, and CEL stands for carbon equivalent of the liquid. In addition, the liquidus temperature, TL , is given by, TL (in C) = 1669 - 124 CEL (9.67)

(Note: For comparison of various studies on TL versus CEL see reference 62, p. 655.)

Consequently, a simple cooling curve allows one to determine TL from the austenite arrest
temperature and hence the CEL for the cast meta!. This result only tells us that the there is some

composition lies along some particular line on the composition plane. Because this line is
not quite parallel to the CE line (which defines eutectic compositions)

ambiguity in using the CEL to determine whether or not an iron is hypo- or hyper-eutectic.
For example, a 2% Si iron becomes hypereutectic (CE > 4.3) at a CEL of 4.12, and a 3% Si iron at a CEL of 4.05. Assuming all cast irons have Si " 3% as shown on Fig. 9.73, a CEL < 4.05 will assure a hypoeutectic iron, whereas for 4.05 < CEL < 4.26 one cannot be sure the iron is hypoeutectic, based only on the CEL determination. In a majority of cases the cooling curve can be used as a process control device to insure that the liquid composition is holding close to the desired value and this is standard practice in many foundries.

When the phosphorous content of the iron becomes significant it is necessary to

modify the relationship for CE and CEL as follows, Eutectic Trough: Austenite Liquidus C + 1/3 Si + 1/3 P = 4.25 C + 1/4 Si + 1/2 P = CEL (9.68) (9.69)

11

._-_._--

-------------

In a relatively recent development the British Cast Iron Research Association,

BCIRA, has shown how one

, , ,

may estimate the carbon concentration of the melt in hypoeutectic irons by utilizing
both the liquidus and the

'-,..........

, , , ,
, , , ,

Liquidus Isotherms

eutectic arrest temperatures. As

may be seen on Fig. 9.87, if

one solidifies

an iron of
l\

composition Co, the liquid may follow a variety of paths down to the eutectic temperature, such as a-lor a-2. The path will

I', , ,) .... ' -,::.....0:_-

,.

.e

depend on growth rate and

gradient and should be fairly

constant for constant cooling conditions. Using a commercially available resin

bonded sand cartridge with an embedded thermocouple (known as Tectips') they have shown63 that the temperature of

,,~:S;
4 phase plane
Projection of Liquidus Isolherms

the liquidus and eutectic are related to the alloy composition

of the starting alloy by the two

;< /.
/

%C +1 %Si::: CEL 4 /

/.

I.:

1ection ofE~~ Trough e 1 e onto composlIion plane:

equations,

%C+ i%Si=4.2S
Figure 9.87. S~limJ of Fe-C-Si 1e11ltUJ imporlalllfor JlIUkrslandUIg solidiflallion if cast irOft.f.

TL = 1650 - 121 C - 26.62 (Si + 2.45 P) TE = 1104 - 9.8 C - 12.05 (Si + 2.44 P)

(9.70) (9.71)

In these experiments the sand cartlidges were coated with a tellurium wash which has been found to inhibit the gray eutectic reaction and cause the white eutectic (Fe + Fe3C) to form. This has the advantage that it extends the composition range where both an austenite and a eutectic arrest are observed. It may be seen that the final terms in brackets in Eqns. (9.70) and (9.71) are essentially identical so that one may combine them and solve for the carbon

content.
%C = 0.0155 TE - 0.00701

TL - 5.53

(9.72)

Hence, from the cooling curves obtained with a tellurium coated Tectip one may obtain the

carbon content of the iron using Eqn. 9.72.

BCIRA introduced this method in 1973 and it is now widely used. They have further modified Eqns. (9.70) to (9.71) by additional studies and these results are available to members as Report 1120, September 1973. It may be seen from Eqns. (9.70) and (9.71) that one may eliminate C and thereby obtain the Si content from the cooling curve if

the P content is known.

Results at BClRA show that the carbon content may be

determined to an accuracy of 0.1 % and in irons of low phosphorus content to an accuracy of 0.14%. 'Trade name of Leeds and Northrup

.05%) the Si

12

Additonat References 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. A. Moore, AFS Transactions Sj, p. 268 (1973) and Brit. Foundryman (1974). J. F. Wallace, AFS Transactions
R. W. Heine, AFS Cast Metals Research J., p. 49 (June 1971).

V.lL Patterson and M. J. Lalich, AFS Transactions.8li, p. 33 (1978).

sa. p. 59

JU. p. 75 (1975).

R. Hummer, The Metallurgy of Cast Iron, p. 147, Georgi Pub. Co., SL Saphorin, Switzerland, 1975. E. R. Evans and J. V. Dawson, AFS Int. Cast Met. J., p. 13 (June 1976). I. Riposan and L. Sofroni, AFS Int. Cast Met. J., p. 23 (March 1978). The Metallur~ of Cast iron. p. 655, Georgi Pub. Co., St. Saphorin, Switzerland, 1975. A. Moore, Foundry Trade Journailli, p, 885 (December 1971).

A. Moore, AFS Cast Metals Research J., p. 15 (March 1972).

13